Nobody knows the what the least painful way to die is, because all the people who would have experienced the various ways of dying, would have died. Hence we don't know which ways are the least painful. However, I would suggest that the quickest and least painful way of dying is in your sleep, of old age.
Other quick ways of dying include being shot in the head or heart, high speed car crash without a seat belt, and jumping off a very tall object without a parachute.
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